Thioalkylphenyl carbamates

ABSTRACT

1. A COMPOUND OF THE FORMULA   1-R1,2-R2,3-R3,4-(H3C-S-X-),5-(H3C-NH-COO-)-BENZENE   WHEREIN X IS 1-(METHOXYMETHYL)-1,3-PROPYLENE AND R1, R2 AND R3 ARE INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND LOWER ALKYL.

United States Patent @ffice 3,849,477 Patented Nov. 19, 1974 3,849,477 THIOALKYLPHENYL CARBAMATES Edward D. Weil, Lewiston, and Hans L. Schlichting,

Grand Island, N.Y., assignors to Hooker Chemical Corporation, Niagara Falls, N.Y.

No Drawing. Continuation of application Ser. No.

612,064, Dec. 1, 1966, which is a division of application Ser. No. 262,376, Mar. 4, 1963, now Patent No. 3,331,894. This application May 13, 1969, Ser. No. 826,076

Int. Cl. C07c 149/42 US. Cl. 260479 C 2 Claims ABSTRACT OF THE DISCLOSURE There is provided a compound of the formula CON (Lmveralkyl) H2.

wherein:

(a) n is an integer from 1 to 2;

(b) X is an alkylene group of from 2 to 8 carbon atoms;

(c) R R and R are independently selected from the group consisting of hydrogen and lower alkyl;

(d) the sulfur atom is separated from the phenyl ring by at least two carbon atoms; and

(e) R is of 1 to about 20 carbon atoms and is selected from the group consisting of:

(1) hydrocarbyl selected from the group consisting of alkyl, alkenyl, cycloalkyl, phenyl, naphthyl, alkylphenyl, benzyl, and arylalkyl; and

(2) acyl selected from the group consisting of alkanoyl, benzoyl, thiobenzoyl, cyano, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, N-alkylthiocarbamoyl, N,N-dialkylthiocarbamoyl, and O alkylthiocarbonyl.

The compound of this invention finds utility as insecticides.

and to methods for pest control utilizing said composio tions. More specifically, the invention relates to novel N- lower-alkyl-substituted carbamates of thioalkylphenols.

The novel compositions of the present invention are represented by the following formula ON (lower alkyl) nHZ-n X-S O -R Rla wherein the substituent X is a substituted or an unsubstituted alkylene radical having at least two carbon atoms, said alkylene radical preferably having from 3 to 8 carbon atoms, the sulfur atom attached to said alkylene radical being separated from the phenyl ring by at least two carbon atoms, preferably by 3 to 8 carbon atoms, R R and R are substituents individually selected from the group consisting of hydrogen and lower alkyl radicals, R is a substituent selected from the group consisting of hydrocarbyl and acyl, p is an integer from 0 to 2, inclusive,

p being 0 when R is acyl and n is an integer from 1 to 2, inclusive, preferably 1.

The term lower alkyl is meant to encompass alkyl radicals having from 1 to about 6 carbon atoms, said radicals being branched or unbranched.

For reasons of cost and the like, the lower alkyl radical on the carbamate nitrogen is preferably methyl.

The term acy as used herein refers to the radical obtained by removal of the OH group from an acid.

The term hydrocarbyl as used herein represents the radical obtained by removal of the hydrogen atom from a hydrocarbon and thus encompasses alkyl, alkenyl, cycloalkyl, phenyl, naphthyl, alkylphenyl, benzyl, and other arylalkyl. The preferred hydrocarbyl radicals are those having from 1 to about 20 carbon atoms.

The alkylene group X may be unsubstituted or may be substituted by lower alkyl, hydrocarbyloxymethyl, hydrocarbylthiomethyl, hydrocarbyloxy, 2-(hydrocarbyloxy) ethyl, or Z-(hydrocarbylthio)ethyl.

The compositions of the present invention are useful for their insecticidal activity toward a large variety of insects (including mites) and against other invertebrate animal pests such as spiders, millipedes, slugs, and nematodes. The compositions of the invention also have unusual repellent properties toward various insects. Further, the compositions of the present invention have useful systemic properties in plants, i.e., the ability to translocate from the site of application to other parts of the plant where insects are located.

Illustrative examples of the X substituents include isoamyl, tert-amyl, l-ethylpropyl and hexyl. It is to be substituted alkyl such as allyl, methoxyethyl, hydroxyethyl, chloropropyl. Further, the R substituent can be aryl, L

such as phenyl, tolyl, tert butylphenyl, p-chlorophenyl, 2,4,5-trichlorophenyl, or arylalkyl such as benzyl, 2-phenylethyl, p-chlorobenzyl, o-methoxybenzyl, or acyl such as acetyl, propionyl, butyryl, benzoyl, thiobenzoyl, cyano, N-

methylcarbamoyl, N-methylthiocarbamoyl, N,N-dimcthyl-,

carbamoyl, N,N-dimethylthiocarbamoyl, other N- and N,N-hydrocarbyl-substituted carbamoyl and thiocarbamoyl, dimethoxyphosphinyl, diethoxyphosphinyl, dimethoxythiophosphinyl, diethoxythiophosphinyl, other di(lower alkoxy)-phosphinyl and -thiophosphinyl and O-alkylthiocarbonyl.

-It is, of course, appreciated that the substituent X can be other hydrocarbyl and acyl groups without departing from the scope of the instant invention.

For reasons for high pesticidal activity and ease of manufacture by applicants copending process of Ser. No. 262,375, filed Mar. 4, 1963, certain species are preferred. The preferred group is encompassed by the formula:

C-CONHCHa CHCH2CH2SOpR I B l 2 a 2 wherein the substituents R R and R are as above defined, R is a substituent selected from the group consisting of hydrogen, lower alkoxymethyl and 2-(lower-alkoxy) ethyl, and R is a substituent selected from alkyl, phenyl, benzyl, acetyl, and di(lower alkoxy)thiophosphinyl, p being an integer from to 2 when R is selected from phenyl, benzyl, and alkyl, and p being 0 when R is selected from acetyl and di(lower alkoxy)thiophosphinyl. The preferred alkyls, as already mentioned above, have from 1 to 20 carbon atoms.

Examples of compounds of this preferred group are those of the detailed examples given below as well as the following:

2-(3-methylthiopropyl)-3-methyl-5-isopropylphenyl N-methyl carbamate;

2-(3-methylthiopropyl)-5-tert-butylphenyl N-methyl carbamate;

2-(3-methylthiopropyl)-5-( 1-ethylbutyl)phenyl N-methyl carbamate;

2- 3-methylthiopropyl -3,4,5-trimethylphenyl N-methyl carbamate;

2-(3-methylthio-l-[ethoxymethyl]propyl) phenyl N-methyl carbamate;

2-(3-methylthio-1-[hexyloxymethyl]propyl) phenyl N-methyl carbamate;

2-( 3-isopropylthiol- 2-butoxyethyl] propyl) phenyl N-methyl carbamate;

2-(3-octylsulfinylpropyl) phenyl N-methyl carbamate;

2-(3-octadecylsulfonylpropyl phenyl N-methyl carbamate;

2-(3-diamyloxythiophosphinylthiopropyl) phenyl N-methyl carbamate; and

2- 3-phenylsulfonylpropyl) -4-methylphenyl N-methyl carbamate.

The N-methylcarbamates of the present invention are prepared from the corresponding phenols by (1) reaction with methyl isocyanate, (2) reaction with methylcarbamyl chloride (preferably in the presence of one molar equivalent of an HCl-acceptor such as caustic soda, triethylamine, or the like, or (3) reaction with phosgene to form the chloroformate, followed by reaction with methylamine to replace the chlorine atom.

The composition of the present invention wherein the integer p is 1 or 2 may be thus made from the corresponding phenols, in which case no further reaction step is necessary, or may be made from the less oxidized phenol sulfide having a lower value of p, in which case the required additional oxygen atoms are replaced on the sulfur after carbamylation by subsequent oxidation by one or two molar equivalents (as required) of a suitable sulfide oxidizing agent, for example, hydrogen peroxide, peracetic acid, performic acid, perbenzoic acid, chromic acid, or molecular oxygen in the presence of a catalyst (such as N3O4)- The compounds of the less preferred group, where n is 2 and/or the lower alkyl group on the nitrogen is other than methyl, are prepared in analogous ways. For example, reaction of o-(3-methylthiopropyl) phenol with ethyl isocyanate yields the corresponding N-ethylcarbamate, and reaction of this phenol with dimethylcarbamyl chloride in the presence of one molar equivalent of triethylamine gives the corresponding N,N-dimethylcarbamate.

While the compositions of the instant invention may be utilized as pesticides in the pure form, they may be conveniently employed in the form of formulations which, in many instances, enhance pesticidal activity. Suitable formulations include solutions of the pesticide composition in solvents such as petroleum hydrocarbons, e.g., xylene, heavy aromatic naphthalenes and the like, and aqueous dispersions or emulsions generally containing surface active agents such as those listed in Soap and Chemical Specialties, vol. 3, No. 7, pp. 50-61, No. 8, pp. 48- 61, No. 9, pp. 52-67, and No. 10, pp. 38-67 (1955). Also useful are solid formulations of the compositions of the instant invention. For example, solid carriers such as talc, silica, clay, vermiculite and the like may be utilized in the formulation. The solid formulations may also contain surface active agents, sticking agents, stabilizing agents, or binders to facilitate their application.

The composition of the present invention may further be formulated with other pesticides, for example, fungicides, such as sulfur, the fungicidal dithiocarbamates, dodecyl quanidine, nitropolychlorobenzenes and various fungicidal compositions containing chlorinated alkyl thio groups, such as captan. Further, the compositions of the present invention may be formulated with other insecticides and acarcides, such as DDT, lindane, methoxychlor, parathion, methyl parathion, malathion, sulfur, pyrethrins, bis(pentachlorocyclopentadienyl) other chlorinated insecticides, phosphate insecticides and the like.

Further, the compositions of the present invention may be formulated with synergists that serve to enhance the pesticidal activity, for example, piperonyl butoxide and the like. It is, of course, appreciated that any pesticidal composition may be used in combination with the compositions of the present invention which may serve to enhance, complement, or synergize said compositions.

The method of using these pesticides is to apply them to the locus of the pests to be controlled, preferably at rates of about 0.05 to 20 pounds of active ingredient per acre in the case of surface application to crops, or when admixed with a medium such as soil, water, or air, concentrations of 0.1 to 1,000 parts per million may be employed, depending on the nature of the pest involved, duration of pesticidal effect required, nature of the medium, and other factors, such as weather conditions.

In order that those skilled in the art may better understand the present invention and the manner in which it may be practiced, the following specific examples are given.

In the examples, specification and claims, all parts are by weight and all temperatures are in degrees centigrade, unless otherwise indicated.

EXAMPLE 1 o-(3-methylthiopropyl)phenyl N-methylcarbamate A mixture of 2.2 parts of o-(S-methylthiopropyl)phenol, prepared as described in applicants application Ser. No. 262,375, filed on even date herewith, 1 part of methyl isocyanate and 0.01 part of dibutyl tin dilaurate catalyst was allowed to stand at 35 C. for 5 hours, then stripped free of unreacted isocyanate by applying a vacuum of 0.1 millimeters of mercury pressure at to C. for 1 hour. The product was obtained as a residual oil, nearly colorless and moderately viscous, exhibiting the characteristic carbamate infrared absorption bands at 5.8 microns (carbonyl) and 3 microns (NH). On standing, the oil solidified to a crystalline solid, melting point 38 to 40 C., having the correct nitrogen analysis for C H O NS.

5 6 EXAMPLES 2 TO 27 EXAMPLE 29 Substantially the procedure of Example 1 was followed, with minor modifications in regard to temperature, time and use of solvent. In all cases, a catalytic amount, 0.1 to 1 percent, of dibutyl tin dila-uratc was employed. The conditions of the reactions and the properties of the products obtained thereby are presented in the following tables.

Aphicidal activity Nasturtium plants heavily infested with aphids (Aphis 5 fabae) were sprayed with 0.1 percent aqueous dispersions CH N C O Reac- Reac- Analysis used tion tion Ex. (parts by temp. time Description (and parts by wt.) of Empirical N N N o. Phenol used (parts by weight) weight) 0.) (hrs) N -metliylcarbainate obtained formula calcd. found 2 o-(3-aeetylthiopropyl) phenol (5.3)- 2 Reflux Viscous straw-colored oil (6.7) C13H1103Ns 5. 25 5. 06 3. o-(dliethiniyghgopliosphinylthiopropyl)- 2 Reflux Viscous reddish oil (6.0) O15H2403Ns2 3, 72 3, 2

p eno 5.55 4. o-(3-ethylthiopropyl) phenol (5). 2 40 18 Clear nearly-colorless oil (5.5) OBHHOZNS 5. 4 5, 5 o-(3-n-butylthiopr0pyl) phenol (5) 2 40 18 d0 CH2302NS 4.97 4.71 6 o-(3-tert-butylthiopiopyl) phenol (5) 2 40 18 Coloi-)le5s 5c)rystals, mp. 67 (from hex- C15H2302NS 4. 97 5.17

9.116 7 o-(3-n-octylthiopropyl) phenol (5) 2 40 18 Light amber oil (5.5). CIQH3102NS 4. 56 4. 00 8.. o-(3-benzylthiopropyl) phenol (5) 2 40 18 Clear viscous syrup (5 C1 H 1O NS 4,44 4.12 9.. o-(3-dodecylthiopropyl) phenol (5) 2 40 18 Clear o l (5.2) CzaHsnOzNS 3. 5G 3. 39 o-(3-phenylthiopropyl) phenol (5) 2 40 18 Clear light amber syr CnHmOzNS 4. 64 4. 35 11..- o-(S-methylthiopropyl)-p-cresol (2.57)-. 1.5 35 18 Colorless crystals, mp 53 CrgHwOzNS 5.5 6.0

(from heptane-benzene) (2). 12 2,6-di(3-methylthiopropyl) phenol (4.5). 2 30 18 Colorless oil (5.3) C H2 O2NS 4, 3 4,7 13.-." o-(3-methylthiobutyl) phenol (2.2) l. 5 30 18 Colorless viscous syrup (2.5) CmHmOzNS 5. 5 5. 1 14. o-(3-methylthiopropyl)-m-ercsol (2).... 2 5 1 do C13H1902NS 5.5 5,7 15 2-(3-methylthiopropyl)-3,5-xylenol (1.7). 2 25 12 Colorless viscous syrup (2) C12I'I1502NSO1 5.12 5. 01 16 2- (3- methylthiopropyD-4-eliloroplieno 5 25 12 Colorless crystals, mp. 65-60" (from C12H1602NSC1 5.12 5.01

(6). benzene-heptane) (5). 17 2-(3-met1hylthiopropyD-3,5-diisopropyl- 10 25 12 Clear viscous syrup (7) CI H O NS 4, 3 4,3

heno 18..." o-glmetliylsulfinylpropyl)phenol (5.97). 3 25 12 Viscous tan HzO-sol. syrup (7.5) Ci2H 703NS 5. 49 5. 87 19 o-(3-ethylsulfinylpropyl)phenol (4 plus 2 25 12 Viscous colorless syrup (3.1) CIQHNOQNS 5. 21 4. 92

10 parts benzene). 20 0-(3 n butylsulfiiiylpropyl)phenol (3 2 2 12 d0 C1 H2 0 NS 4. 71 4. 61

plus 10 parts benzene). 21 o-(3 octy1sulfinylpropyl)phenol (6.7 plus 1 12 Viscous colorless syrup (6.8) ClQIIalOQNS 3. 9 4, 0

parts benzene 22 0 (3 henylsulfinylpropyl) phenol (7.8 1 25 12 Viscous colorless syrup (8.8) C1 H O NS 4, 42 4.82

plus 5 parts benzene 23 o-(3-methylsulfonyslpropyl) phenol (5 plus 3 25 12 Brownish viscous syrup (5.9) C12H704NS 5. 2 5. 5

10 parts benzene 24. o-(3- methylsulfinylpropyD- pcresol (10 5 25 48 Viscous yellowish syrup (10.5) O H1 O NS 5. 21 5. 12

plus 20 benzene). I 25--. o-(2-methylthiopropyl) phenol (7) 5 25 12 Viscous colorless syrup CuHnOzNS 5. 81 5.71 26 o-(1-methyl-7-methylthioheptyl) phenol 5 25 12 ...do C17H2102NS 4. 51 4. 61

10 27 o-(3-methylthio-1-[methoXymethyl] pro- 5 25 12 Viscous amber syrup C H O NS 49 4,5

pyl) phenol (10).

EXAMPLE 28 50 of the various compounds. After 24 hours, the percentage Miticidal activity kill was observed.

Bean plants (Tendergreen variety) infested with about Chemical: Percent aphid km 100 mites per leaf (adult two-spotted mites of Terranyohus o (3 methylthiopropyl)phenyl Ndmethylcarbaf spp.) were sprayed with 0.1 percent aqueous disp rsions mate 1 100 of the various test chemicals. After 24 hours, the perz (3 methylthiopropyl) p cresy1N methy1car centage m te klll was 0bS61'V6d, Wlllh t f ll g results: bamate 100 Chemical: Percent mite kill 0-(0,0-dimethylthiopropyl)phenyl N methylo-(3 methylthi0pr0pyl)phenyl N-meth- 100 (82 at carbamate 100 ylcarbamate 0.01%). o-(3-methylthio 1 [2-methoxyethyl1propyl) o-(3-methylthio 1 [methoxymethyl] phenyl N-methylcarbamate 100 propyl) phenyl N-methylcarbamate 100. 0-(3-methylsulfinylpropyl)phenyl N methyl- 0 (diethoxythiophosphinylthiopr py carbamate 100 p y N-methylcarba'mate o-(3-methylsulfonylpropyl)phenyl N methylo-(3 octylthiopropyl) phenyl N-meth- @arbamate 1 ylcafbaimatc. o-(3-diethoxythiophosphinylthiopropyl) phenyl y p py )p 100 N-methylcarbamate 1 ylcarbamate 1 A1 so 100 percent kill when same amount of chemical was 'P Y P P phenyl dispersed in the soil in which the nasturtiuins were rooted.

ylcarba-mate 95. (Systemic test.) o-(3-acetylthiopropyl) phenyl N-rnethylcarbamate 40, Even at 0.025 percent concentration o-(3-methylth1oo-(3-methy1thio) phenyl N-inethylcarpropyDphenyl N-methylcarbamate continued to give 100 bamate 1 0. percent kill, whereas o-(methylthio) phenyl N-methylcarbamate gave only 42 percent kill of Aphz's fabae.

1 For comparison.

7 EXAMPLE 30 Housefly control Various compounds of the invention were sprayed as 1 percent, and 0.1 percent aqueous dispersions onto caged housefiies (Musca domestica). At 2 hours and 24 hours after spraying, the effect was observed, with the following results:

At 1 At 0.1 Chemical Observation pcrccnt percent o-(dimethoxythiophosphinylthio- 2 hr. KD 100 100 propyDphcnyl N -metliylcarba- 24 hr. kill 100 100 mate.

-(3-mcthylthiopropyl)phenyl 2 hr. KD 100 95 N -mcthylcarbamate. 24 hr. kill 100 85 o-(3-ethylthiopropyl) phenyl 2 hr. KD 100 65 N -mctl1ylcarba.mate. 24 hr. kill 100 100 o-3-n-butyltl1iopropyl) phenyl 2 hr. KD 100 95 N -metliylcarbamate. 24 hr. kill 100 95 o--3-n-octylthiopropyl) phenyl 2 hr. KD 100 35 N-mcthylcarbamate. 24 hr. ki1l 100 60 o-(3-phcnyltl1iopropyl)phenyl 2 hr. KD. 100 45 N-mctliylcarbamute. 24 hr. kill- 100 70 o-(3-benzyltl1iopropyl)phenyl 2 hr. KD 100 85 N-mcthylcarbamatc. 24 hr. kill 100 90 o-(3-tert-butylthiopropyl)phenyl 100 55 N -mcthylcarbamate. 100 S0 2-(3-mcthyltl1iopr0pyl)phenyl 2 hr. KD 75 0 N -metl1ylcarbamate. 24 hr. kill 85 75 2- (3ethylsulfinylpropyl) phenyl 2 hr. KD 85 0 N-methylcarbmnate. 24 hr. kill 95 30 2-(3-methylthiopropyl)-3,5-di- 2 hr. KD. 100 100 mcthylphenyl N -methylcarba- 24 hr. kill. 100 100 mate.

*KD =knockdown.

The compositions of the invention also show repellency toward some insect species as demonstrated by the following example:

EXAMPLE 31 Insect repellency EXAMPLE 32 An emulsifiable concentrate was prepared by blending the following ingredients:

Pounds Carbamate product of Example 1 2.0 Emcol H300X 0.1 Emcol HSOOX 1 0.1

Xylene to total volume of 1 gallon.

Commercial emulsifiers manufactured by Witco Chemical Company: blends of alkylaryl sulfonate salts with polyoxyethylene ethers.

This concentrate was emulsified with water prior to application to lima bean plants with aphid control.

EXAMPLE 33 A wettable powder formulation was prepared by blending and grinding together the following ingredients in a hammer mill:

Pound Carbamate product of Example 2 1.00 Sorbit P (alkylarylsulfonate wetting agent) 0.05 Marasperse N (lignin sulfonate dispersing agent) 0.05 Microcel E (synthetic silicate carrier) 0.90

The resultant powder was dispersed in water by gentle agitation before spraying onto cotton plants for general insect control.

While there have been described various embodiments of the invention, the methods and elements described are not intended to be understood as limiting the scope of the invention, as it is realized that changes therein are possible, and it is further intended that each element recited in any of the following claims is to be understood as referring to all equivalent elements for accomplishing substantially the same results in substantially the same or equivalent manner, it being intended to cover the invention broadly in whatever form its principle may be utilized.

What is claimed is:

1. A compound of the formula FOREIGN PATENTS 10/1961 France 260-479 12/1962 Great Britain 260-479 OTHER REFERENCES Metcalf Pest Control, vol. 30, pp. 20, 26, 28 (June 1962).

JAMES A. PATTEN, Primary Examiner 

1. A COMPOUND OF THE FORMULA 